Azo dyestuffs



United States Patent 3,152,114 AZODYESTUFFS Edgar Siege] and Manfred Still, Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengese lsehait, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Jan. 26, 1960, Ser. No. 4,628 Claims priority, application Germany Jan. 31, 1959 11 Claims. (Cl. 26(l157) The invention relates to new azo dyestuffs; more particularly it relates to azo dyestufis of the formula In this formula R stands for hydrogen, a lower alkyl, benzyl, phenyl, COOH, COOCH and COOC H group, R means a lower alkylene radical with 24 car bon atoms between N and X, X stands for Cl, Br, OSO Y or a sulfonyl hydroxy group, Y being hydrogen or an alkali metal cation, R represents the residue of a diazo compound, i.e., a moiety selected from the group consisting of a carbocyclic and a heterocyclic diazo components, and n means one of the integers 1 to 3.

It is an object of the invention to provide valuable azo dyestufis; a further object is the provision of dyestuffs which are particularly suitable for the dyeing of cellulose-containing materials; still another object is to provide dyestuffs which yield dyeings on cellulose of excellent wet fastness properties.

The new dyestuffs are obtainable by coupling diazotised amines of the aromatic or heterocyclic series, in the 4-position, with pyrazolones of the following composition In the formula R, R and X have the above significance.

The process for the production of the new dyestuffs can also be varied by first coupling a diazotised amine of the aromatic or heterocyclic series with a pyrazolone of the formula in which R and R have the above-mentioned significance, and by converting in the resultant azo compound the hydroxyl group of the l-positioned hydroxyalkyl radical in the pyrazolone nucleus into the substituent X by usual processes.

Amines suitable as diazo components are aromatic carbocyclic diazo components, for example, aminobenzenes such as 1-aminobenzene-3-sulphonic acid, l-aminobenzene-3,5-disulphom'c acid, 4-aminodiphenyl-3-sulphonic acid, 1-amino-4,5dichlorobenzene-Z-sulphonic acid or anthranilic acid; aminonaphthalenes such as Z-aminonaphthalene-d-sulphonic acid or 2-aminonaphthalene-4,8-disulphonic acid, amino group-containing heterocycles the amino group of which is diazotisable, for example azole diazo components, such as, 2-amino-1,3,5-thiodiazole, 3- amino-1,2,4-triazole, 2-aminobenzthiazole or 6-methyl-2- (4-aminophenyl)-benzthiazolesulphonic acid; further tetrazo components, such as 4,4'-diaminodiphenyl, 4,4- diaminodiphenyl-2,2'-disulphonic acid, 4,4-diamino-5,5'- dimethoxydiphenyl-Z,2'-disulphonic acid, 4,4-diaminostilbene-2,2'-disulphonic acid, 4,4-diaminodibenzyl-2,2-di- Patented Oct. 6, T984 sulphonic acid, 3,3'-diamino-dibenzenesulphimide or 4,4- diamino-diphenylsulphone; compounds having more than two diazotisable amino groups are also applicable, for example the conversion product of copper phthalocyanine tIior tetra-sulphochloride with 3 or 4 mols of l,3-diaminobenzenel-sulphonic acid or 1,4-diaminobenzene-3- sulphonic acid.

The pyrazolones according to the formula HO GR CH2CH O-SO CH The radical R may be varied in the indicated manner.

The coupling is carried out in a weakly acid to alkaline aqueous or organic medium. Depending on the components used which may contain solubilising groups such as sulphonic acid or carboxylic acid groups, azo dyestuifs are obtained which difier in their Water-solubility. Dyestufis are especially valuable which contain in the molecule several of the said pyrazolone coupling component. Dyestuffs of this kind are obtained by conversion of the pyrazolone coupling components with tetrazoor poly-diazo compounds.

The new dystuifs are suitable for the dyeing of the most varied materials, especially for the dyeing and printing of hydroxyl group-containing textile materials of natural or regenerative cellulose. Dyeing or prints are obtained on these materials which are outstandingly fast to Washing and to boiling by applying the dyestufis to the dyeing material and subjecting the dyeing goods to the action of acid binding agents, preferably at an elevated temperature.

For dyeing, the dyestuffs are preferably used in an aqueous solution which can be treated with alkaline substances such as alkali metal hydroxide or alkali metal carbonate, or compounds convertible into Weakly alkaline substances such as alkali metal bicarbonate. Further auxiliary agents can be added to the solution provided they do not react with the dyestuffs in an undesirable manner. Such additives are, for example, surface-active substances such as alkyl sulphates, substances which prevent migration of the dyestufis or dyeing assistants such as urea (for improving the solubility and fixation of the dystutls), or inert thickening agents such as oil-in-water emulsions, tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes thus prepared are applied to the dyeing material, for example by padding in a foulard or by printing, and subsequently heating to an elevated temperature, preferably 40150 C., for some time. Heating can be carried out in a hotfiue, steaming apparatus, on heated rollers or by introduction into hot concentrated salt baths alone or consecutively in any desired sequence.

When a padding liquor or dyebath is used without alkali, a passage of the dry goods through an alkaline solution to which common salt or Glauber salt is added follows. The addition of salt reduces migration of the dyestuif from the fibre.

It is also possible to treat the dyeing material first with one of the aforementioned acid binding agents, then with the solution or paste of the dyestufi and finally, as indicated, to fix the dyestufi at an elevated temperature.

After fixing is completed, the dyeing goods are rinsed hot and, in cases where it is necessary, the dyed material is finally soaped whereby insufiiciently fixed dyestuff is removed. Dyeings having excellent wet fastness are ob tained.

For printing materials containing hydroxyl groups or amide groups, a printing paste is used consisting of the dyestuff solution a thickening agent such as sodium alginate and an alkaline compound or a compound splitting oif alkali upon heating such as sodium carbonate, potassium carbonate or sodium bicarbonate, and the printed material is rinsed and also finally soaped.

Amide group-containing material such as wool, silk and the like can be dyed in a preferably neutral medium.

The dyeing process is suitably followed by a washing operation in a neutral or alkaline aqueous bath.

Provided that the new dyestuifs are sufficiently watersoluble they can be applied for dyeing or printing from an aqueous solution. Water-insoluble dyestufis of the type as defined by the invention are advantageously applied in a finely dispersed form.

The following examples are given for the purpose of illustrating the invention.

Example 1 17.3 parts by weight of 3-aminobenzene sulphonic acid and 6.95 parts by weight of sodium nitrite are dissolved in 200 parts by volume of water with the addition of a little sodium carbonate at pH 7-8; 28 parts by volume of concentrated hydrochloric acid are added with stirring and cooling with ice. Excess nitrous acid is removed with amido-sulphonic acid after 10 minutes. The clear diazo solution is run into a solution of 29 parts by weight of the hydrobromide of l-(B-bromethyl)-3-methyl-5-pyrazolone in 150 parts by volume of water and 150 parts by volume of a saturated sodium acetate solution, while cooling with ice. Stirring is continued at pH 4-5 for another 1-2 hours and the clear yellow solution is completely evaporated to dryness in a vacuum. The residual mixture contains about 35% of the dyestutf of the formula l CHTCHT-BP and inorganic salts and is used directly for dyeing.

ing of very good fastness to Wet treatment, rubbing and light is obtained.

Example 2 17.1 parts by weight of 4,4-diamino-diphenyl-2,2'-disulphonic acid and 6.95 parts by Weight of sodium nitrite are dissolved in 200 parts by volume of water with the addition of a little sodium carbonate at a pH of 7-8, 28 parts by volume of concentrated hydrochloric acid are added with ice-cooling and the mixture stirred for 30 minutes. After the diazo suspension is freed from excess nitrous acid with amidosulphonic acid, it is run with icecooiing into a solution of 29 parts by weight of the hydrobromide of 1-( B-bromethyl)-3-methyl-5-pyrazolone in 150 parts by volume of water and 150 parts by volume of a saturated sodium acetate solution. Coupling is rapidly completed at a pH of 5 and the mixture stirred for a further hour. The resultant dyestuif of the formula is salted out by the addition of 100 parts by weight of common salt, filtered off with suction, washed with a dilute common salt solution and dried either in the air or in a vacuum drying oven at 40 C.

A fibre material of regenerated cellulose is impregnated at 20-25" C. with a solution containing per litre of liquor 15 g. of the dyestuif obtained according to the aforesaid instruction, as well as 50 g. of urea and 20 g. of sodium carbonate. The fabric is subsequently squeezed to a moisture content of about 100%, intermediately dried at 50-60 C. and steamed at 105 C. for 8 minutes in a steaming apparatus. oughly rinsed with hot water and treated at boiling temperature for 20 minutes with a solution containing per litre 5 g. of Marseilles soap and 2 g. of sodium carbonate. After rinsing and drying an intense yellow dyeing of very good fastness to wet treatment, rubbing and'light is obtained.

Example 3 18.6 parts by weight of 4,4-diamino-dibenzyl-2,2'-disulphonic acid and 6.95 parts by Weight of sodium nitrite are dissolved in 200 parts by volume of water with the addition of a little sodium carbonate at a pH of 7-8, 28 parts by volume of concentrated hydrochloric acid are added while cooling with ice and the mixture stirred for 30 minutes. After the diazo suspension is freed from excess nitrous acid with amidosulphonic acid, it is run with ice-cooling into a solution of 29 parts by weight of the hydrobromide of 1-(B-bromethyl)-3-methyl-5-pyrazolone in 150 parts by volume of water and 150 parts by volume of a saturated sodium acetate solution. Coupling I is rapidly completed at a pH of 5 and the mixture stirred for a further hour. The resultant dyestuff of the formula A cotton fabric is impregnated at 20-25 C. with a solution containing per litre of bath 20 g. of the above dyestulf and 0.5 g. of a non-ionic wetting agent (e.g., a poly-hydroxyethylatecl oleyl alcohol) as well as 100 g. of urea and 20 g. of sodium hydroxide. The fabric is then squeezed between two rubber rolls to a moisture content of about 100%. After intermediate drying at 50-60 C. the fabric is heated to 140 C. for 10 minutes and the dyeing thus obtained thoroughly washed with hot water, and then treated at the boil with a solution containing per litre 5 got Marseilles soap and 2 g. of sodium carbonate.

is salted out by the addition of 100 parts by weight of common salt, filtered off with suction, washed with a dilute common salt solution and dried either in the air or in a vacuum drying oven at 40 C.

The same dyestuff may be obtained in the following manner:

18.6 parts by weight of 4,4'diamino-dibenzyl-2,2'-disulphonic acid are diazotized in the manner described above, and the suspension of the diazo compound is run into a solution of 14.5 parts by weight of l-(B-hydroxyethyl)-3-methyl-5-pyrazolone in 150 parts by volume of After rinsing and drying a somewhat greenish yellow dye- Water and parts by volume of a saturated sodium ace- The dyeing thus obtained is thortate solution. Coupling is rapidly completed at a pH of volume of water and 150 parts by volume of a saturated 5. The mixture is stirred for a further hour and then sodium acetate solution. Coupling is rapidly completed re-acidified with hydrochloric acid to a pH of 34. The at a pH of 5 and the mixture stirred for a further hour. precipitated dyestufi' is filtered off with suction, washed The resultant dyestuff of the formula 011 0 SO Na N COH HO-O N SOsNa OCH: t t CHrGHr-BI CHg-CHgr-Bl' with water and dried at 80 C. The dry dyestutf is finely is salted out by the addition of 100 parts by weight of powdered and stirred in a mixture of 100 parts by volume common salt, filtered 01f with suction and dried either of concentrated hydrobromic acid (d 1.5) and parts in the air or at C. in a vacuum drying oven.

by volume of concentrated sulphuric acid under reflux 15 A cotton fabric is padded with a neutral solution con- (at 127 C.) for 8 hours. After cooling, the dyestuff is taining per litre 15 g. of the dyestufi obtained, squeezed precipitated from the orange-coloured suspension by the to a moisture content of 100%, dried at 60 C. padded addition of 250 parts of a saturated common salt solution, again with a cold solution containing per litre 300 g. of filtered oil with suction, washed with an acidified dilute common salt and 20 g. of sodium hydroxide, again common salt solution and either dried in the air or in 20 squeezed to a moisture content of about and heated avacuum at 40 C. to C. for 10 minutes. After rinsing, soaping at the 15 g. of the dyestuil' obtained according to the process boil, renewed rinsing and drying, an intense reddish yellow described above are mixed with 100 g. of urea, 300 ml. dyeing of very good fastness to wet processing and rubof water are then added at 40 C. and the mixture is bing and good fastness to light is obtained. stirred until the dyestuii is completely dissolved. This 29 Exam le 5 solution is slowly stirred in 500 g. of a sodium alginate p thickening (60 g. of sodium alginate per kg. of thicken- Parts y Wfiight 0f the tri-(amillo-sulphophenyling), the mixture is made up with cold wate t a tot l sulphonamide), described below, and built up from copweight of 960 g. and 20 g. of sodium hydroxide dissolved per phthalocyanine and 6.95 parts by weight of sodium i 20 1 f water are dd d t th i t 30 nitrite are dissolved in 500 parts by volume of water with A cottgn fabric is printed with the rgsultant printing H16 addition Of a llttlfi sodium carbonate at a PH Of 7-8, paste dried, steamed at 105 C. for 8 minutes and further and t m r s n cooled to C- The blue t t d as l, A d ll i t f very d f tsolution is then slowly run with stirring and ice cooling ness to wet processing, rubbing and light is obtained. into a miX tuI@ 28 Parts y Volume of conctfmrated Exam [8 4 hydrochlorlc acid and 200 parts by weight of 166, the

p green barely soluble diazo compound thus being instanta- 20.l parts by weight of 4,4-diamino-5,5'-dimethoxyneously formed. It is stirred with ice cooling for 30 diphenyl-2,2-disulphonic acid and 6.95 parts by weight minutes, the excess nitrous acid removed with amidosulof sodium nitrite are dissolved in 200 parts by volume phonic acid and the diazo suspension combined with of water with the addition of a little sodium carbonate at stirring and ice cooling with a solution of '29 parts by a pH of 7-8, 28 parts by volume of concentrated hydroweight of the hydrobromide of l-(fi-bromethyl)-3-methylchloric acid are added with ice cooling and the mixture S-pyrazolone in parts by volume of water and 150 stirred for 30 minutes. After the diazo suspension is free parts by volume of a saturated sodium acetate solution. of excess nitrous acid with amidosulphonic acid, it is run Coupling is rapidly completed at a pH of 5. The mixture into a solution of 29 parts by weight of the hydrobromide 45 is stirred for a further hour and the green dyestufi of the of l-(B-bromethyl)-3-methyl-5-pyrazolone in 150 parts by formula I C Hr-OHg-BI is salted out by the addition of 100 parts by weight of common salt, filtered oil with suction, washed with a dilute common salt solution and the product is dried either in the air or at 40 C. in a vacuum.

The triamine used may be prepared by introducing 1 mol of copper phthalocyanine-tretrasulphochloride into an ice-cold solution of 8 mol of 2,4-diaminobenzene-sulphonic acid and 400 parts by Weight of sodium acetate in 8000 parts by volume of water, stirring at room temperature and a pH of 5 for hours, after neutralizing with sodium carbonate stirring at a pH of 7 for a further two hours and finally stirring the mixture rendered strongly sodium-alkaline at 80 C. for a half hour. The copper phthalocyanine-triamine is isolated by acidifying the clear blue solution with concentrated bydrochloric 0 acid and filtration of the precipitated dyestufi.

A cotton fabric is treated according to the instructions given in Example 1 with a solution containing per litre of liquor 15 g. of the above dyestufi as well as the additives mentioned in Example 1. The cotton fabric is then dyed in bright yellowish green shades of very good fastness of wet treatment and rubbing and of good fastness to light.

Example 6 18.5 parts by weight of 4,4'-diaminostilbene-2,2-disulphonic acid and 6.95 parts by weight of sodium nitrite are dissolved in 200 parts by volume of water with the addition of a little sodium carbonate at a pH 7-8, 28 parts by volume of concentrated hydrochloric acid are added with ice cooling and the whole stirred for minutes. After the diazo suspension is freed from excess nitrous acid with amidosulphonic acid, it is run into a solution adding a total of g. of common salt in several portions, then adding 10 g. of sodium hydroxide, raising the temperature to about 95 C. and maintaining at this temperature for 30 minutes. After rinsing, soaping at the boil and drying an orange dyeing is obtained having a very good fastness to wet processing and to rubbing.

Example 7 If in Example 5 46.9 parts by weight of the copperphthalocyanine tri-(aminosulfophenyl)-sulfonamide are replaced by 44.7 parts by weight of the 1,4-diaminoanthraquinone derivative described below and otherwise proceeding in the same manner a green dyestuir' of the following structure is obtained:

SON

a a N The diamino-anthraquinone derivative to be used in this example is prepared by stirring a cold aqueous solution of excess 2,5-diaminobenzene-sulfonic acid with the disulfochloride which has been prepared by action of chlorosulfonic acid upon l,4-di-(3'-methylphenylamino)- anthraquinone.

Cotton fabric is treated according to the process described in Example 1 with a solution which contains 15 g. of the above dyestufi' per litre and the additives indicated in Example 1. Clear green shades are thus obtained or" very good fastness to wet processing and to rubbing.

Example 8 In the process of Example 3 29 parts by weight of the hydrobromide of l-(B-bromoethyl)-3-methyl-5-pyrazolone are replaced by 16.1 parts by weight of l-(B-chloroethyl)-3-methyl-5-pyrazolone. The yellow dyestuif of the following formula is obtained:

N C-OH I I HOC N N I C of 29 parts by weight of the hydrobromide of l-( s-bromethyl)-3-methyl-3-pyrazolone in 150 parts by volume of water and 150 parts by volume of a saturated sodium acetate solution. The coupling is rapidly completed at a pH 5 whereupon the mixture is stirred for another hour.

The resultant dyestuif of the formula is salted out by the addition of 100 parts by weight of SOaNB. NaO S The pyrazolone derivative may be produced by treating 1-( IS-hydroxyethyl)-3-methyl-5-pyrazolone with a mixture of concentrated hydrochloric acid and concentrated sulfuric acid.

A cotton fabric is printed according to the method indicated in Example 3 with a printing paste containing 20 g. of the above mentioned dyestufi per kg, damped common salt, filtered off with suction, washed with a dilute and aftertreated in usual manner. A greenish yellow common salt solution and dried in the air or at 40 C. in a vacuum drying oven.

50 g. of a cotton skein are dyed in 1 litre of a dye bath which contains 1.5 g .of the above dyestufi by raising the print is thus obtainable which exhibits very good fastness to Wet processing, rubbing and to light.

If Example 3 the pyrazolone coupling component is replaced by 22.5 parts by weight of the sulfuric acid temperature from 20 to about 80 C. within 30 minutes, semi-ester of 1-(B-hydroxyethyl)-3-methyl-5-pyrazolone a yellow dyestufi having the following structure is obtainsodium nitrite. After removal of exceeding nitrous acid able: with amido sulfonic acid the tetrazonium solution is al- N oon S|O N \T 1 HOC N f 3- L 21 a \N CHrCHz-OSO N3 JHrCH OSO3Na The dyestutf is isolated by adding concentrated hydro- 10 lowed to run while cooling with ice into a solution of 29 chloric acid to the reaction mixture until strong acid parts by Weight of the hydrobromide of l-(fi-bromoethyD- medium is attained and subsequently salting out with 3-methyl-5-pyrazolone in 150 parts by volume of water common salt. The product thus obtained is yellowish and 150 parts by volume of concentrated sodium acetate brown colored and is mixed with about 40 parts by Weight solution. The coupling is finished at pH 5 and the preof solid sodium acetate and dried. cipitated dyestutf of the formula l CHafi-gN=NQON=N(HJ-fiCHa N C-OH H ON C C1 t t CH CH Br CH CHzBr A cotton fabric is printed in accordance with the profiltered with suction, Washed with water and air-dried or cedure described in Example 3 with a printing paste dried at 40 C. in vacuo. The dyestufi may be used-in containing 40 g. of the dyestuif/sodium acetate mixture the same manner as the product in the preceding exper kg, steamed and aftertreated in customary manner. amples.

Example 11 One obtains a yellow prmt having very good fastness to Wet processing and to rubbing. 18.6 parts by weight of 4,4'-d1amm0d1benzyl-2,2'- Example 9 disulfonic acid (component A) and 6.95 parts by Weight of sodium nitrite are dissolved with the addition of 32 parts by Weight of 2-(3-sulfo-4'-aminophenyl)-6- some soda at pH 7 to 8 in 200 parts by volume of water. methylbenzthiazole and 6.95 parts by Weight of sodium. 28 parts by volume of concentrated hydrochloric acid nitrite are dissolved with the addition of some soda at are added while cooling with ice and stirring is continued pH 7 to 8 in 200 parts by volume of Water; 28 parts 35 for 30 minutes. After removal of the excess nitrous acid by volume of concentrated hydrochloric acid are added 39.5 parts by weight of the sodium salt of 2-(3-methylwhile cooling with ice and the mixture is then stirred 5'-aminobenzoyl) amino 5 hydroxynaphthalene-7-sulfor 30 minutes. Excess nitrous acid is then destroyed fonic acid (component B) and 21 parts by weight of with amido sulfonic acid and the diazonium salt solution calcinated soda in 1000 parts by volume of water are allowed to run With ice cooling into a solution of 29 added while cooling with ice. The coupling sets in immeparts by weight of the hydrobromide of l-(B-bromodiately at a pH of about 8. The dyestufi which after ethyl)-3-methyl-5-pyrazolone in 150 parts by volume of completion of the coupling is completely precipitated is Water and 150 parts by volume of concentrated sodium filtered by suction, washed with dilute sodium chloride acetate solution. The coupling is completed at pH 5 solution and again pasted with 1000 parts by volume of and the precipitated dyestufi of the formula Water and 28 parts by volume of concentrated hydro- \I chloric acid. While cooling with ice a solution of 6.9

/\ parts by weight of sodium nitrite is added and the reaction mixture stirred for 2 hours to complete the dia- CH H [L zotisation'. excess of nitrous acid is destroyed with S qIOaNa armdo sulfomc acid and then a solution of 29 parts by L weight of the hydrobromide of 1-(B-bromoethyD-3- methyl-S-pyrazolone (component C) in 150 parts by OHFCHFBI volume of water and 15 0 parts by volume of concentrated filtered with suction, washed with dilute sodium chloride sodium acetate solution added with cooling. The consolution and dried. pling is soon complete and stirring then continued for A fabric of natural or regenerated cellulose is dyed 1 hour. The dyestulT thus formed corresponds to the according to the method described in Example 1 with a formula solution which contains 15 of the above d estuff er litre and the additives menti ned in the dyeing procediire and is nearly completely preclpltated' It can be filtered in Example 1. Reddish yellow shades are thus obtained by Fuctlon P after thoroughly washing with diluted which distinguish themselves by ery g d fasmess to SOdIllm Chlm'lde solution air-dried OI dried at 40 C. in Wet processing and to rubbing. vacuo.

Example 10 A cotton fabric is treated in accordance with the 12 65 parts by Weight of 4 2, dich1om method described in Example 1 with a solution which diphenyl in 200 parts by Volum of Water diazotisfid contains 15 g. of the above said dyestufi and the additives with ice cooling by means of 28 parts by volume of conused in the dyeing FY04:ess of Example The fabIiC is centrated hydrochloric acid and 6.95 parts by volume of then thoroughly soaped at the boil, brilliant somewhat yellowish red shades thus being obtained of very good We claim: fastness to wet processing and to rubbing. 1. An azo dyestuif of the formula If processing in the manner described above with the use of the components A, B and C listed in the following table one likewise obtains red to yellowish red dye- 5 130-0 N stuffs which in accordance with the dyeing and printing processes shown in Examples 1 to 6 yield dyeings and I CH prints on cellulose containing fibrous material of good fastness properties, particularly of very good fastness to CH2 wet processing. 10 Br .1

Shade of the dyeing on cellulose Component A Component B Component C 4,4-diamino-dibenzyl-2,2-disulf0nic 2-(3'-arninobenzoyl)-amino- Hydrobromide of the Yellowish red.

acid. 5-hydroxynaphthalene-7- l-(fl-bromoethyD-Lisultonic acid. inethyl-dpyrazoone. Do 2-(4-aminophenyl suldo D0. ionyl)-amino(5-hydroxynarhthalenefl-sulfonic aci Succinic acid-N,N-di-(4'-amino-3- 2-((4-aminophenylacetyl)- do Bluish red.

4-aminobenzoyl)-amino- 5-hydroxynaphthalene-7- sulfonic acid. 2-(4-amino-phen0xyaccty1)- do Yellowish red.

amino-.E-hydroxy-naphthaleneJ-sulfonic acid.

sulfophenyD-amide.

4,4-diamino-dlphenyl-2,2-disultonic acid.

Ethylenediamine-N,N-di(4- 2-(4-aminophenylacetyl)- do Orange.

aminophenyD-sulfonamide. amino-5-hydroxynaphthalene-7-sulfonic acid. 2,4-bis-(4-aminobenzyl-amino)-6- 2-(4-aminophenylacetyl)- do Yellowish red.

(fi-sulfoethyl-amino)-1,3,5- amino-.S-hydroxynaphtriazine. tha1ene-7-sulfonic acid.

Example 12 34.2 parts by weight of 4,4'-diamino-diphenyl-2,2- disulfonic acid and 13.9 parts by weight of sodium nitrite are dissolved while adding some soda at pH 7 to 8 in 400 parts by volume of Water, and 56 parts by volume of concentrated hydrochloric acid are added with cooling'. The reaction mixture is stirred for minutes and excess nitrous acid then removed by adding amido sul- 40 fonic acid. A solution of 29 parts by weight of the hydrobromide of l-(fl-bromoethyl) 3 methyl-S-pyrazolone in 200 parts by volume of water is then added with ice cooling. The pH value of the strong mineral acid mixture is increased to a pH of 2 to 3 by means of adding crystallised sodium acetate with stirring. After stirring for 1 hour with ice cooling the yellow diazomonoazo compound is obtained.

The mixture is then adjusted with soda to pH 5 and allowed to run with stirring in the ice cold solution of 30.2 parts by weight of the sodium salt of succinic acid- N,N'-di-(5-hydroxy-7-sulfonaphthyl-[2])-amide and 22 parts b i ht f l i t d d i 600 parts b 6. A dyestufl? according to claim 1 wherein R stands V l e f Wat r- A PH 8 the pling has rapid y for a disulfo-dibenzyl moiety as a diazo compound and completed. The dyestufi? thus formed corresponds to the n for 2. 5

wherein R is a member selected from the group consisting of an aromatic carbocyclic diazo component and an azole diazo component, and n stands for a whole number within the range of 1-3.

2. A dyestufi according to claim 1 wherein R stands for a benzene moiety as a diazo component and n stands for the integer 2.

3. A dyestuif according to claim 1 wherein R stands for a stilbene moiety as a diazo component and n stands for the integer 2.

4. A dyestuff according to claim 1 wherein R stands for a diphenyl moiety as a diazo component and n stands for the integer 2.

5. A dyestuif according to claim 1 wherein R stands for a dibenzyl moiety as a diazo component and n stands for the integer 2.

7. The dyestuif which in the free acid state corresponds to the formula and is completely precipitated in the cold while adding common salt, filtered by suction, washed with dilute sodium chloride solution and dried at 40 C. in vacuo. t-

A cotton fabric is treated according to the method indicated in Example 1 with a solution which contains I N 15 g. of the dyestufl? mentioned above. Clear yellowish a N red shades of very good fastness to wet processing and CHzCHz-Bl to rubbing are thus obtained.

14 8. The dyestufi which in the free acid state corre- 10. The dyestuif whch in the free acid state corresponds to the formula sponds to the formula Hogs soar:

| OCHa SOaH CH C--GN=N-ON=NCCCH3 5 l I Q, 1 U, CH;-C-CN=N N=NC--CCH:

N N N 0-011 HO-C N I l 011,011,131? CH CH Br f N l 9. The dyestuif which in the free acid state corre- 10 CHBCHZ'BI' sponds to the formula 11. The dyestufi which in the free acid state corresponds to the formula References Cited in the file of this patent UNITED STATES PATENTS 1,775,605 Schweitzer Sept. 9, 1930 1,973,635 Lantz Sept. 11, 1930 FOREIGN PATENTS 406,532 Italy Dec. 2, 1943 791,443 Great Britain Mar. 5, 1958 1,140,191 France -July 16, 1957 OTHER REFERENCES Guthrie: American Dyestuif Reporter, January 7, 1952, pp. 13-14 and 30.

Wagmann: Texti1-Praxis, 1958, October, pp. 1056- 1061. 

1. AN AZO DYESTUFF OF THE FORMULA 